Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
l-ARYL- Q2-1,2,4-TRIAZOLIN-5-ONES COMPOUNDS
AS INTERMEDIATES
The invention described in this application
pertains to weed control in agriculture, horticulture,
or other fields where there is a desire to control
unwanted plant growkh. More speciEically, the present
application describes novel herbicidal l-aryl-~2-1,2,4-
triazolin-5-ones, herbicidal compositions containing the
new compounds, methods for preparing the compounds, and
methods for preventing or destroying undesired plant
growth by preemer~ence or postemergence application of
the herbicidal compositions to the locus where control
is desired. The present compounds may be used to
effectively control a variety of both grassy and
broadleaf plant species.
Various herbicidal l-aryl-~2-1,2,4-triazolin-5-
ones are known in the art. U.S. Patent No. 4,318,731
and corresponding British Patent No. 2,056,971 disclose
herbicidal aryltriazolinone~ of the formula
Cl R2
J~l.=~ ~1
wherein Rl is alkyl, R2 is a hydrogen, alkyl, or
alkenyl, and X is hydroxy, alkyl, or alkoxy, alkoxy-
alkoxy, alkenyloxy, or alkyloxycarbonylalkyloxy.
British Patent No. 2,090,250 add~ to the
~.
~ 3
- 2 -
above genus compounds wherein R2 is alkynyl,
halomethyl, or haloethyl, and X is alkoxy, alkenyl-
oxy, alkynyloxy, alkoxyalkoxy, hydroxy, halomethyl-
oxy, or haloethyloxy.
European Patent Application Publication No.
55,105 discloses a series of herbicidal aryltria-
zolinones of the formula
F O
wherein R is alkyl, alkenyl 9 or cycloalkyl, X is
chlorine or bromine, and Y is hydrogen or alkoxy.
l~ Japanese Kokai 81-32,468 discloses herbicidal
aryltriazolinones of the formula
Cl O
Cl ~ N ~
wherein R is hydrogen, alkyl, or 2-propenyl, and
Rl i 5 methyl or alkoxy.
South African Patent Application No. 78/3182
discloses herbicidal aryltriazolinones of the
formula
,~JJ~ _ R
n~l I =~
-- 3
wherein Rn is hydrogen or represents 1 to 4 same
or different radicals selected from halogen, nitro,
cyano, optionally halo-substituted alkyl, alkoxy,
or alkylthio, and optionally substituted phenyl or
phenoxy, and Rl is alkyl, alkoxyalkyl, dialkoxy~
ethyl, dialkylaminoethyl, or cycloalkyl.
U.S. Patent No. 4,315,767 discloses herbicidal
bicyclic compounds of the following formula
~ Q
XJ~N 1~c~2 ) /
wherein V is hydrogen, halogen, methyl, or alkoxy,
X is hydrogen, halogen, cyano, methyl, methoxy, or
nitro, Y is hydrogen, halogen, or methyl, m and n
are 0 to 4 (m plus n is 2 to 4), Q is oxygen or
sulfur, and Z is oxygen, S(O)p, or NRl wherein
p is 0-2 and Rl is alkyl, provided that when m
plus n is 2 or 4 then Y and X are other than hydro-
gen, and when Z is S(O)p then n is 1 to 4.
Additional herbicidal bicyclic compounds based
on the aryltriazolinone nucleus are disclosed in
U.S. Patent No. 4,213,773 and have the following
structural formula
Y t~
CH2)n
(CH3)m
7~'~
-- 4
wherein V is hydrogen, halogen, hydroxy, alkyl, or
-ORl; Rl is optionally substituted alkyl,
cycloalkyl, cycloalkylalkyl, optionally substituted
alkenyl, alkynyl, optionally substituted benzyl,
alkylaminocarbonyl, talkyl)(me-thyl or methoxy)-
aminocarbonyl, acyl, alkoxycarbonyl, or -CHR7R8
wherein R7 is hydrogen or alkyl and R8 is
cyano, acetyl, hydroxycarbonyl, alkoxycarbonyl,
hydroxymethyl, alkoxymethyl, alkylcarbonyloxy-
methyl, hydroxycarbonylethenyl, alkoxycarbonyl-
ethenyl, or a group -C0-NRllR12 wherein Rll
is hydrogen, alkyl, alkenyl, or alkoxy, and R12
is hydrogen or alkyl; X is halogen, cyano, methyl,
methoxy, or nitro; Y is hydrogen9 halogen, or
me~hyl; Z is hydrogen or halogen; n is 3-5; m is
0-2; and Q is oxygen or sulfur, with certain pro-
vi sos .
A class of ~ -1,2,4-triazolin-5-ones is dis-
closed as fungicides in U.S. 4,098,896. The dis-
closed genus has the formula
R S;- ~ ~ R
1 ~ 2
SR
wherein R is alkyl, alkenyl, alkynyl, cycloalkyl,
or optionally substituted phenyl or arylalkyl, Rl
is haloalkyl or haloalkenyl, and R2 is optionally
substituted alkyl, alkenyl, or alkynyl, or option-
ally substituted aryl, arylalkyl, or alkylaryl.
-- 5
The compounds of this invention are l-[4-
bromo-2-fluoro-5-(substituted)oxyphenyl]-3-methrl-
4-difluoromethyl- -1,2,4-triazolin-5-ones of the
formula
F
3r ~ ~- CHF2
RO CH3
wherein R is alkyl, alkenyl, alkynyl, alkoxyalkyl,
or alkyl-S(O)n-alkyl wherein n is O ~o 2.
The present compounds are named in accordance
with the numbering system shown in formula I, for
the ring atoms of the heterocycle which is the same
as the numbering system used in U.S. 4~318,731,
supra, for similar compounds.
A subgenus of this invention comprises the
compounds of formula I in which R is selected from
-CH39 -C2H5' -CH(CH3)2~ -CH2cH3~ CH2CH2 3
-CH(CH3)CH20CH3, -CH2CH=CH2, -CH2C--CH, and
-CH(CH3)C-CH.
The presence of a bromine atom at ~he C-4
position of the phenyl ring in formula I was found
to generally give superior cotton selectivity in
preemergence applications at application rates at
which a variety of weeds are controlled. A
preferred aspect of the invention comprises the
compounds in which R is selected from -CH3,
-C2H5, -CH(CH3)2, -CH2ocH3~ C~l2CH2 3'
-CH2C_CH, and -CH(CH3)C-CH. In a preferred specific
embodiment, R is selected from -CH3, -CH20CH3,
and CH2C--CH.
The present compounds, which have a fluorine
atom at the C-2 position of the phenyl ring9 in
- 6 ~ 3~
general have herbicidal properties far superior to
those o~ tne corresponding compounds having a chlo-
rine atom at C~2 of the phenyl ring, and are highly
active at low application rates against a variety
of grassy and broadleaf weed species in both pre-
emergence and postemergence applications.
The compounds of this invention may be pre-
pared by methods analogous to the methods described
in -the references above for similar compounds or by
methods within the skill of the art.
The compound of formula I in which R is hydro-
gen is an important intermediate to the herbicidal
compounds of formula I in which R is as defined
above, as illustrated in Examples 2-7 below. Other
compounds useful as intermediates are the compounds
corresponding to formula I in which the -CHF2 sub-
stituent is replaced with a hydrogen atom, as il-
lustrated in Example lH below.
Preparation of the present compounds is illus-
trated in the following examples. All temperatures
show-n are in degrees Celcius, and reduced pressures
for concentration of liquid were produced by a vac-
uum pump.
EXAMPLE 1
PREPARATION OF 1-(4-BROMO-2-FLUORO-5-
~ETHOXYPHENYL)~3-METHYL-4-DIFLUOROMETHYL-
-1,2,4-TRIAZOLIN-5-ONE
. _
Step A 2-Bromo-4-fluorophenyl methyl carbonate
A stirred solution o~ 561 g (5.0 moles) of
4-fluorophenol in 600 mL of dioxane was cooled in
an ice-water bath and 831 g (5.2 moles) of bromine
was added dropwise. The complete addition required
~ 2
1.5 hours, during which the reaction mixture tem-
perature was maintained at 14-25C. Following the
addition, the ice-water bath was removed, and the
reaction mixture temperature rose to 35C. The
reaction mixture was stirred for two hours, then
600 mL of water, followed by 520 mL of 10.8N
aqueous sodium hydroxide were added dropwise over
30 minutes and 1 hour respectively. Upon complete
addition, the reaction mixture was cooled to
0-10C, and 591 g (6.15 moles) of methyl chlorofor-
mate was added dropwise over four hours. Upon
complete addition, the reaction mixture was allowed
to warm to ambient temperature and was stirred for
17 hours. After this time, 450 g of aqueous 50%
sodium hydroxide was added to neutralize the reac-
tion mixture. The resultant solid was collected by
filtration, and the filter cake washed with two 500
mL portions of water. The solid was dried under
reduced pressure to give 1211 g of 2-bromo-~-
fluorophenyl methyl carbonate; m.p. 75-78C.
The nmr spectrum was consistent with the pro-
posed structure.
Step B 2-Bromo-4-fluoro-5-nitrophenyl methyl
carbonate
A rapid]y stirred solution of 946 g (3.8
moles) of 2-bromo-4-fluorophenyl methyl carbonate
in 1292 mL of sulfuric acid was cooled to 5-10C,
and 368 g ~4.18 moles) of 70% nitric acid was added
dropwise over two hours. Upon complete addition,
the reaction mixture was allowed to warm to ambient
temperature and was stirred for two hours. The
reaction mixture was poured into 5000 mL of ice
water. Any material remaining in the reaction
vessel was washed into the ice-water with 750 mL of
water. The resultant solid was collected by fil-
tration and washed with 1000 mL of water. The
solid was dried with mild heat under reduced pres-
sure to give 1031 g of Z-bromo-4-fluoro-5-nitro-
S phenyl methyl carbonate.
The nmr spectrum was consistent with the pro-
posed structure.
Step C 2-Bromo-4-fluoro-5-nitrophenol
A stirred solution of 1031 g (3.5 moles) of
2-bromo-4-fluoro-5-nitrophenyl methyl carbonate in
3000 mL of 2.3N aqueous sodium hydroxide was heated
to reflux and stirred for three hours. The hot
reaction mixture was filtered through diatomaceous
earth. Any material remaining in the reaction
vessel was washed onto the filter cake with lO00 mL
of water. The filtrate was cooled to 8-10C, and
560 mL of concentrated hydrochloric acid was added,
with stirring, over Qne hour. The resultant solid
was collected by filtration. Any material remain-
ing in the reaction vessel was washed onto the
filter cake with 1000 mL of water. The dried
filter cake was recrystallized from toluene to
give, in two crops, 543 g of 2-bromo-4-fluoro-5-
nitrophenol, m.p. 12~-126C.
The nmr spectra were consistent with the pro-
posed structure.
Step D 4-Bromo-2-fluoro-5-methoxynitrobenzene
A stirred solution of 30.0 g (0.127 mole) of
2-bromo-4-fluoro-5-nitrophenol, 26.9 g (0.19 mole)
of methyl iodide, and 26.3 g (0.19 mole) of potas-
sium carbonate in 200 mL oE acetone was heated at
reflux or five hours. The reaction mixture was
~ 8 3 ~
g
filtered, and the filtrate concentrated under
reduced pressure ~o give a residue. The residue
was dissolved in methylene chloride and passed
through a column of silica gel. The eluate was
concentrated under reduced pressure to give 30 g of
4-bromo-2-fluoro-5-methoxynitrobenzene; m.p.
74-76C.
Step E 4-Bromo-2-fluoro-5-methoxyaniline
To a stirred solution of 30.0 g (0.12 mole) of
4-bromo-2-fluoro-5-methoxynitrobenzene in 200 mL of
acetic acid was added 40 mL of water, followed by
the portionwise addition of 30.0 g (0.54 mole) of
- iron filings during a 2.5 hour period. Upon com-
plete addition, the reaction mixture was stirred at
25-35C for one hour. Diethyl ether, 200 mL, was
added, and the reaction mixture was filtered
through a pad of diatomaceous earth. The filtrate
was washed with 200 mL of water. The organic layer
was separated and neutralized with solid sodium
bicarbonate. The mixture was dried with magnesium
sulfate and filtered. The filtrate was concen-
trated under reduced pressure to give a residual
solid. The solid was recrystallized from petroleum
ether to give 23.5 g of 4-bromo-2-fluoro-5-methoxy-
aniline; m.p. 60-62C.
Step F Pyruvic acid, 4-bromo-2-fluoro-5-methoxy-
phenylhydrazone
IJnder a nitrogen atmosphere, a stirred solu-
tion of 23.5 g (0.107 mole) of 4-bromo-2-fluoro-5-
methoxyaniline in 150 mL of concentrated hydro-
chloric acid was cooled to -9C, and a solution of
7.4 g (0.107 mole) of sodium nitrite in 40 mL of
2'73~
- 10 -
water was added dropwise over two hours. Upon com-
plete addition, the reaction mixture was stirred at
-9C for 45 minutes, then a solution of 36.0 g
(0.160 mole) of stannous chloride in 50 mL of con-
centrated hydrochloric acid was added dropwise overone hour. The reaction mixture temperature was
maintained at -9 to 0C throughout the addition.
Upon complete addition, the reaction mixture was
allowed to warm to ambient temperature and was
stirred for two hours. After this time, 100 mL of
water was added to the reaction mixture, followed
by the dropwise addition of a solution of 9.4 g
(0.107 mole) of pyruvic acid in 100 mL of water.
Upon complete addition, the reaction mixture was
stirred for 30 minutes at ambient temperature. The
reaction mixture was filtered to collect a solid.
The solid was dried to give 23.5 g of pyruvic acid,
4-bromo-2-fluoro-5-methoxyphenylhydrazone;
m.p. 15~-158C.
~ Step G 1-(4-Bromo-2-fluoro-5-methoxyphenyl)-3-
methyl-~2-1,2,4-triazolin-5-one
A stirred solution of 22.7 g (0.074 mole) of
pyruvic acid, 4-bromo-2-fluoro-5-methoxyphenyl-
hydrazone, 20.5 g (0.074 mole) of diphenylphos-
~5 phoryl azide, and 7.5 g (0.074 mole) o triethyl-
amine in 150 mL of toluene was heated at reflux for
four hours. The reaction mixture was cooled and
diluted with diethyl ether. The mixture was
extracted three times with aqueous 1 molar sodium
hydroxide. The combined extracts were washed with
diethyl ether and made acidic with concentrated
hydrochloric acid. The resultant solid was
collected by filtration and washed with water. The
solid was dried to give 15.0 g of 1-(4-bromo-2-
fluoro-5-n~ethoxyphenyl)-3-methyl-~2-1,2,4-
triazolin-5-one.
The nmr spectrum was consistent with the
proposed structure.
Step H 1-(4-Bromo-2-fluoro-5-methoxyphenyl)-3-
methyl-~-difluoromethyl-~2-1,2,4-
triazolin-5-one
A stirred solution of 15.0 g tO.050 mole) of
1-(4-bromo-2-fluoro-5-methoxyphenyl)-3-methyl-
~2-1,2,4-triazolin-5-one, 5.6 g tO.10 mole) of
potassium hydroxide, and 1.6 g ~0.005 mole) of
tetrabutylammonium bromide in 150 mL of tetrahydro-
furan was saturated with gaseous chlorodifluoro-
methane. The reaction mixture was stirred at
ambient temperature for 16 hours. An additional
2.9 g (0.052 mole) of potassium hydroxide was
added, and the reaction mixture was again saturated
with chlorodifluoromethane. Upon complete satura-
tion, the reaction mixture was stirred for two
hours, then diluted with diethyl ether. The mix-
ture was washed with water, then with aqueous
saturated sodium chloride. The organic layer was
dried with sodium sulfate, filtered, and the fil-
trate concentrated under reduced pressure to give a
residue. The residue was subjected to column
chromatography on silica gel. Elution was accom-
plished with 2:1 methylene chloride:petrol0um
ether The appropriate fractions were combined and
concentrated under reduced pressure to give 4.2 g
of 1-(4-bromo-2-fluoro-5-methoxyphenyl)-3-methyl-
4-difluoromethyl-~2-1,2,4-triazolin-5-one;
m.p. 129-130C.
The nmr and the ir spectra were consistent
with the proposed structure.
o~7
- 12 -
Analysis calc'd for CllHgBrF3N302:
C37.52, H 2.58, N 11.93;
Found: C37.38, H 2. 35, ~ 52.
EXAMPLE 2
PREPARATION OF 1-(4-BROMO-2-FLUORO-5-~ETHOXY-
METHOXYPHENYL)-3-METHYL-4-DIFLUOROMETHYL-~2-
1 2 4-TRIAZOLIN-5-ONE
,
Step A 1-(4-Bromo-2-fluoro-5-hydroxyphenyl)-3-
methyl-4-difluoromethyl-~Z-1,2,~-tria-
zolin-5-one
A stirred solution of 7.3 g (0.029 mole) of
boron tribromide in 30 mL of methylene chloride was
cooled to -40C, and a solution of 3.0 g (0.009
mole) of 1-(4-bromo-2-fluoro-5-methoxyphenyl)-3-
methyl-4-difluoromethyl-Q2-1,2,4-triazolin-5-one
(Example 1) in 25 mL of methylene chloride was
added dropwise. The reaction mixture tempera~ure
was maintained at -40C throughout the addition.
Upon complete addition~ the reaction mixture was
allowed to warm to ambient temperature and was
stirred for 16 hours. The reaction mixture was
poured into ice-water, and the mixture extracted
with die~hyl ether. The extract was dried with
sodium sulfate, filtered, and the filtrate concen-
trated under reduced pressure to give a residue.
The residue was dissolved in diethyl ether, and the
solution was passed through a pad of silica gel.
The eluate was concentrated under reduced pressure
to give Z.9 g of 1-~4-bromo-2-fluoro-5-hydroxy-
phenyl)-3-methyl-4-difluoromethyl-~2-1,2,~-tria-
zolin-5-one.
The nmr and the ir spectra were consistent
with the proposed structure.
- 13 -
Step B 1-(4-Bromo-2-fluoro-5-methoxymethoxy-
phenyl)-3-methyl-4-di~luoromethyl-a2_
1,2,4-triazolin-5-one
To a s~irred suspension of 0.15 g (0.003 mole)
of sodium hydride (50% in mineral oil) in 10 mL of
toluene was slowly added 1.1 g (0.003 mole) of
1-(4-bromo-2-fluoro-5-hydroxyphenyl)-3-methyl-4-di-
fluoromethyl-~2-1,2,4-triazolin-S-one. N,N-di-
methylacetamide (l-Z mL) was added and the reaction
mixture was stirred at ambient temperature until it
~ecame clear. The reaction mixture was cooled to
20C, and 0.8 g (0.006 mole) of methoxymethyl bro-
mide was added. Upon complete addition, the reac-
tion mixture was stirred at ambient temperature for
lg 16 hours. The reaction mixture was poured onto ice
and allowed to stand for one hour. The organic
layer was separated and dried with magnesium sul-
fate. The mixture was filtered, and the filtrate
subjected to column chromatography on silica gel.
Elution was accomplished with 4:1 methylene chlo-
ride:hep~ane. The appropriate fractions were com-
bined and concentrated under reduced pressure to
give 0.9 g o 1-(4-bromo-2-fluoro-5-methoxymethoxy-
phenyl)-3-methyl-4-difluoromethyl-a2-1,2,4-tria-
zolin-5-one as an oil.
The nmr spectrum was consistent with the pro-
posed structure.
Analysis calc'd for C12HllBrF3N3O3:
C 37.72, H 2,89, N 10.99;
Found: C 38.32, H 2.86, N 10.91.
EXAMPLE 3
PREPARATION OF 1-(4-BROMO-2-FLUOR0-5-
PROPARGYLOXYPHE~YL)-3-METHYL-4-DIFLUORO-
METHYL-a 1,2,4-TRIAZOLIN- 5-ONE
A stirred solution of 2.5 g (0.008 mole) of
.
~2~
- 14 -
1-(4-bromo-2-fluoro-5-hydroxyphenyl)-3-methyl-4-di-
fluoromethyl-~2-19294~ triazolin-5-one (prepared
as in Step A, Example 2), 1.6 g (0.01Z mole) of
potassium carbonate, and 1.9 g (0.017 mole) of pro-
pargyl bromide in 30 mL of acetone was heated atreflux for 16 hours. Tlle reaction mixture was
cooled and concentrated under reduced pressure to
give a residue. The residue was dissolved in
methylene chloride and subjected to column chroma-
tography on silica gel. Elution was accomplishedusing methylene chloride. The appropriate frac-
tions were combined and concentrated under reduced
pressure to give 2.3 g of 1-(4-bromo-2-fluoro-5-
propargyloxyphenyl)-3-methyl-4-difluoromethyl-Q2_
1,2,4~triazolin-5-one; m.p. 70-72C.
The nmr spectrum was consistent with the
proposed structure.
Analysis calc'd for C13HgBrF3N3O2:
C 41.51, H 2.41, N 11.17;
Found: C 41.33, H 2.19, N 11.35.
The following compounds were prepared from
1-(4-bromo-2-fluoro-5-hydroxyphenyl)-3-methyl-4-di
fluoromethyl-~2-1,2,4- triazolin-5-one (Example 2A)
by an alkylation procedure analogous to that
described above in either Example 2B or Example 3:
Example 4, 1-(4-BROMO-2-FLUORO-5-ETHOXY-
PHENYL)-3-METHYL-4-DIFLUOROMETHYL-Q -1,2,4-TRIA-
ZOLIN-5-ONE, m.p. 106-108C. The ir and nmr
spectra were consistent with the proposed structure.
Analysis calc'd ~or C12HllBrF3N3O2:
C 39.36, H 3.03, N 11.48;
Found: C 39.65, H 2.82, N 11.22.
Fxample 5, 1-[4-BROMO-2-FLUORO-5-(1-METHYL-
ETHOXY)-PHENYL]-3-~lETHYL-4-DIFLUOROMETHYL-Q -
1,2,4-TRIAZOLrN-5-ONE, obtained as an oil. The ir
and nlnr spectra were consistent with the proposed
f~ 3~
- 15 -
structure.
Analysis calc'd for C13H13BrF3N3O2:
C 41.07, H 3.45, N 11.05;
Found: C 41.03, H 3.19, N 10.93.
Example 6, 1-[4-BROMO-2-FLUORO-5-(1-METHYL-
5 PROPARGYLOXY)PHENYL]-3-METHYL-4-DIFLUOROMETHYL-A2-
1,2,4-TRIAZOLIN-5-ONE, m.p. 80-82C. The ir and
nmr spectra were consistent with the proposed
structure.
Analysis calc'd for C14HllBrF3N3O2:
C 43.10, H 2.84, N 10.76;
Found: C 43.32, H 2.83, N 10.54.
Example 7, 1-[4-BROMO-2-FLUORO-5-(2-METH-
OXYETHOXY)PHENYL]-3-METHYL-4-DIFLUOROMETHYL-~ -
1,2,4-TRIAZOLIN-5-ONE, m.p. 81-82C. The ir and
nmr spectra were consistent with the proposed
structure.
Analysis calc'd for C13H13BrF3N3O3:
C 39.41, H 3.31, N 10.61;
Found: C 39.25, H 3.08, N 10.31.
Herbicidal Activity
The plant test species used in demonstrating
the herbicidal ac~ivity of compounds of this inven-
tion include cotton (Gossypium hirsutum var. Stone-
ville), soybean (Glycine max var. Williams), field
corn (Zea mays var. Agway 595S), rice (Oryza sativa
var. Labelle), wheat (Triticum aestivium var.
Prodax), field bindweed (Convolvulus arvensis),
morningglory (Ipomea Lacunosa or Ipomea hederacea),
velvetleaf (Abutilon theophrasti), barnyardgrass
(Echinochloa crus galli), green foxtail (Setaria
viridis), johnsongrass (Sorghum halepense), and
yellow nutsedge (Cyperus esculentus).
Seeds or tubers of the plant test species were
planted in furrows in steam sterilized sandy loam
soil contained in disposable fiber flats. The
~IL2~i2~73
- 16
flats had been filled to a depth of about 6.5 cm
with the soil. A topping soil of equal portions of
sand and sandy loam soil was placed uniformly on
top of each flat to a depth of approximately 0.5 cm.
The flats for the preemergence tests were
watered, then drenched with the appropriate amount
of a solution of the test compound in a mixture of
acetone and water containing a small amount (up to
0.5% v/v) of sorbitan monolaurate emulsifier/
solubilizer. The concentration of the test
compound in solution was varied to give a range of
application rates~ generally 8.0 kg/ha and sub-
multiplies thereof. The flats were placed in a
greenhouse and watered regularly at the soil
surface for 21 days at which time phytotoxicity
data were recorded.
The flats for the postemergence tests were
placed in a greenhouse and watered for 8-10 days,
then the foilage of the emerged test plants was
sprayed with a solution of the test compound in
acetone-water containing up to 0.5% sorbitan mono-
laurate. After spraying, the foliage was kept dry
for 24 hours, then watered regularly for 21 days,
and phytotoxicity data recorded.
Phytotoxicity data were taken as percent
control. Percent control was determined by a
mèthod similar to the 0 to 100 rating system
disclosed in "Research Methods in Weed Science,"
2nd ed., B. Truelove, Ed.; Southern Weed Science
Society; Auburn University, Auburn, Alabama, 1977.
The present rating system is as follows:
3~
- 17 -
Rating Description
Percent of Main Crop Weed
Control Categories Description Description
0 No effect No crop reduction No weed control
or injury
Slight discoloration Very poor weed
or stunting control
Slight Some discoloration, Poor weed
effect stunting or stand control
Crop injury more Poor to defi-
pronounced but not cient weed
lasting control
-
Moderate injury, Deficient weed
crop usually control
recovers
~loderate Crop injury more - Deficient to
effect lasting, recovery moderate weed
control
Lasting crop Moderate weed
injury no recovery control
Heavy injury and Control somewhat
stand loss less than satis-
facto~y
Severe Crop nearly des- Satisfactory to
troyed a few good weed
survivors control
Only occasional Very good to
live plants left excellent control
100 Complete Complete crop Complete weed
effect destruction destruction
- 18 ~
Herbicidal data are given for various
compounds of the invention in Tables 1 and 2
below. The test compounds are identified in the
tables by Example numbers. In the tables "kg/ha"
is kilograms per hectare and "% C" is percent
control.
TABLE 1
Preemergence Activity
Compound Number* 1 2 3 4
Rate (kg/ha) 0.~625 0.~625 0.~625 0.~625
Species %C %C %C _%C
Cotton 0 0 10 0
Soybean 30 95 80 50
Field Corn 100 100 95 80
Rice 90 95 90 70
~iheat 90 95 95 50
Field ~indweed - 95
l~lorningglory 95 100 90 95
Velvetleaf 100 100 100 100
Barnyardgrass 100 100 100 100
Green Foxtail 90 100 100 100
Johnsongrass 90 95 100 100
Yellow Nutsedge80 - 80 70
Compound Number* 5 6 7
Rate (kg/ha) 0.~625 0.~625 0.~625
sPecies ~ ' %C %C
Cotton 0 10 20
Soybean 10 70 50
Field Corn 80 80 90
Rice 80 95 ~o
Wheat 80 90 ~0
Pield Bindweed - 90
Morningglory 60 90 95
Velvetleaf 100 100 100
Barnyardgrass 80 100 95
Green Foxtail 90 100 100
Johnsongrass 90 100 90
Yellow ~utsedge10 - 90
~The compound number is the number of the Example in
which the particular compound was prepared.
34~
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TABLE 2
Postemer~ence Activity
Compound Number* 1 2 3 5 6
Species 0.~25 0 ~625 0. 625 0. Z5 0. 25
Cotton 70 80 50 80 80
Soybean 90 95 95 80 90
~ield Corn 90 100 100 80 90
Rice 80 100 90 80 95
'~heat 80 95 50 50 95
Field Bindweed - 100 95 90 100
Morningglory100 100 100 80 100
~elvetleaf 100 100 100 100 100
Barnyardgrass90 100 95 80 100
Green Foxtail95 100 100 80 100
Johnsongrass 50 100 80 30 80
Yellow Nutsedge 80
*The compound number is the number of the Example in
which the particular compound was prepared
For herbicidal appliçation, the active com-
pounds as above defined are formulated into herbi-
cidal compositions by admixture in herbicidally
effective amounts with adjuvants and carriers
normally employed in the art for facilitating the
dispersion of active ingredients for the particular
utility desired, recognizing the fact that the
formulation and mode of application of a toxicant
may affect the activity of the material in a given
application. Thus, for agricultural use the pre-
sent herbicidal compounds may be formulated as
granules of relatively large particle size, water-
soluble or water-dispersible granules, as powdery
dusts, as wettable powders, as emulsifiable con-
centrates, as solutions or as any of several otherknown types of formulations, depending on the
desired mode of application.
- 20 ~
For preemergence application ~hese herbicidal
compositions are usually applied either as sprays,
dusts, or granules to the areas in which suppres-
sion of vegetation is desired. For postemergence
control of established plant growth, sprays or
dusts are most commonly used. These formulations
may contain as little as 0.5% to as much as 95% or
more by weight of active ingredient.
Dusts are free flowing admixtures of the
active ingredient with finely divided solids such
as talc, natural clays, kieselguhr, flours such as
walnut shell and cottonseed flours, and other
organic and inorganic solids which act as disper-
sants and carriers for the toxicant; these finely
divided solids have an average particle size of
less than about S0 microns. A typical dust formu-
lation useful herein is one containing 1.0 part of
the herbicidal compound and 99.0 parts of talc.
Wettable powders, also useful formulations for
both pre- and postemergence herbicides, are in the
form of finely divided particles which disperse
readily in water or other dispersant. The wettable
powder is ultimately applied to the soil either as
a dry dust or as an emulsion in water or other
liquid. Typical carriers for wettable powders
include Fuller's earth, kaolin clays, silicas, and
other highly absorbent, readily we~ inorganic
diluents. Wettable powders normally are prepared
to contain about 5-80~ of active ingredient,
depending on the absorbency of the carrier, and
usually also contain a small amount of a wetting,
dispersing or emulsifying agent to facilitate dis-
persion. For example, a useful wettable powder
formulation contains 80.8 parts of the herbicidal
compound, 17.9 parts of Palmetto clay, and 1.0 part
- 21 -
of sodium lignosulfonate and 0.3 part of sulfonated
aliphatic polyester as wetting agents. Frequently,
additional wetting agent and/or oil will be added
to the tank-mix for postemergence application to
facilitate dispersion on the foliage and absorption
by the plant.
Other useful formulations for herbicidal
applications are emulsifiable concentrates. Emul-
sifiable concentrates are hornogeneous liquid or
paste compositions dispersible in water or other
dispersant, and may consist entirely of the herbi-
cidal compound and a liquid or solid emulsifying
agent, or may also contain a liquid carrier, such
as xylene, heavy aromatic naphthas, isophorone, or
lS other non-volatile organic solvent. For herbicidal
application these concentrates are dispersed in
water or other liquid carrier, and normally applied
as a spray to the area to be treated. The per-
centage by weight of the essential active ingre-
dient may vary according to the manner in which thecomposition is to be applied, but in general com-
prises 0.5 to 95% of active ingredien-t by weight of
the herbicidal composition.
Typical wetting, dispersing or emulsifying
agents used in agricultural formulations include,
for example, the alkyl and alkylaryl sulfonates and
sulfates and their sodium salts; polyhydric alco-
hols; and other types of surface active agents,
many of which are available in commerce. The sur-
face active agent, when used, normally comprises 1to 15% by weight of the herbicidal composition.
Other useful formulations for herbicidal
applications include simple solutions of the active
ingredient in a dispersant in which it is com-
pletely soluble at the desired concentration, such
- 22 - ~ ~3
as acetone, alkylated naphthalenes, xylene or other
organlc solvents. Granular formulations, whexein
the to~icant is carried on relatively coarse parti-
cles, are of particular utility for aerial d,stri-
bution or for penetration of cover crop canopy.
Pressurized sprays, typically aerosols wherein the
active ingredient is dispersed in finely divided
form as a result of vaporization of a low boiling
dispersant solvent carrier, such as the Freons, may
also be used. Water-soluble or water-dispersible
yranules are also useful formulations ~or herbici-
dal application of the present compounds. Such
granular formulations are free-flowing, non-dusty,
and readily water-soluble or water-miscible. These
soluble or dispersible granular formulations des-
cribed in U.S. Patent No. 3,920,442, are useful
herein with the present herbicidal compounds.
The active herbicidal compounds of this inven-
tion may be formulated and/or applied with insecti-
cides, fungicides, nematicides, plant growth regu-
lators, fertilizers, or other agricultural chemi-
cals and may be used as effective soil sterilants
as well as selective herbicides in agriculture. In
applying an active compound of this invention, whe-
ther formulated alone or with other agriculturalchemicals, an effective amoun-t and concentration of
the active compound is of course employed.
The active herbicidal compounds of this inven-
tion may be used in combination with other herbi-
cides, e.g. they may be mixed with, say, an equalor larger amount of a known herbicide such as
chloroacetanilide herbicides such as 2-chloro-N-
(2,6-diethylphenyl)-N-(methoxymethyl)ace-tamide
(alachLor), 2-chloro-N-(2-ethyl-6-methylphenyl)-
73'~
~-(2-methoxy-1-methylethyl)acetamide (metolachlor),
and N-chloroacetyl-N-(2,6-diethylphenyl)glycine
(diethatyl-ethyl); benzothiadiazinone herbicides
such as 3-(1-methylethyl)-(lH)-2,1,3-benzothia-
diazin-4-(3H)-one-2,2-dioxide (bentazon); triazine
herbicides such as 6-chloro-N-ethyl-N-(l-methyl-
ethyl)-1,3,5-triazine-2,4-diamine (atrazine), and
2-4-chloro-6-(ethylamino)-1,3,5-triazin-2-ylamino-
2-methylpropanenitrile (cyanazine); dinitrol-
aniline herbicides such as 2,6-dinitro-N,N-di-
propyl-4-(trifluoromethyl)benzeneamine (triflura-
lin); and aryl urea herbicides such as N'-(3,4-di-
chlorophenyl)-N,N-dimethylurea (diuron) and N,N-di-
methyl-N'-3-(trifluoromethyl)phenylurea (fluo-
meturon).
It is apparent that various modifications maybe made in the formulation and application of the
novel compounds of this invention, without depart-
ing from the inventive concepts herein, as defined
in the following claims.
